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Process for preparing substituted glutaric anhydride
CN1274657C
China
Worldwide applications
2004
CN
Application CN 200410041589 events
2004-07-30
2005-04-06
2006-09-13
Application granted
2006-09-13
2024-07-30
Anticipated expiration
Status
Expired - Fee Related
Description
translated from
Technical field
The invention belongs to the preparation method of organic compound, relate generally to the preparation method of substituting group Pyroglutaric acid.
Background technology
1,1-cyclohexanediacetic acid acid anhydride has the group of Pyroglutaric acid, and 3-isobutyl-Pyroglutaric acid also has the group of Pyroglutaric acid.It is a kind of 1 that Chinese patent application 00128111.9 discloses, the preparation method of 1-cyclohexanediacetic acid monoamide, and 1,1-cyclohexanediacetic acid list acyl ammonia is the important intermediate of synthetic antiepileptic drug gabapentin (gabapentin).1,1-cyclohexanediacetic acid monoamide is with 1, and 1-cyclohexanediacetic acid acid anhydride is a raw material, generates 1,1-cyclohexanediacetic acid monoamide with ammonia react under benzene or toluene or xylene solvent existence and 30～110 ℃ of temperature.In this patent application, also mention 1, the preparation method of 1-cyclohexanediacetic acid acid anhydride.Concrete steps are: with 1,1-cyclohexanediacetic acid and excessive acetic anhydride via reaction generate 1,1-cyclohexanediacetic acid acid anhydride, and by-product acetate will obtain 1,1-cyclohexanediacetic acid acid anhydride after acetate and the diacetyl oxide distillation simultaneously.1 of gained, 1-cyclohexanediacetic acid acid anhydride are not only further handled and can be carried out the synthetic 1 of next step, the reaction of 1-cyclohexanediacetic acid monoamide.Above-mentioned 1, the preparation method's of 1-cyclohexanediacetic acid acid anhydride shortcoming raw materials cost is also higher, and the acetate of diacetyl oxide and by-product has certain corrosive nature to equipment simultaneously, and distillment has certain pollution to environment, thereby the aftertreatment workload is bigger.This method also has corresponding description in document GB894385.
Summary of the invention
The purpose of this invention is to provide a kind of cost lower, substantially equipment is not had the preparation method of burn into to the free of contamination substantially substituting group Pyroglutaric acid of environment.
The total technical conceive of the present invention is: be raw material with the substituting group pentanedioic acid directly, dehydration reaction takes place and makes the substituting group Pyroglutaric acid in heating.
A kind of technical scheme that realizes the object of the invention is: have following steps: 1. add reactant substituting group pentanedioic acid in reactor, substituting group pentanedioic acid wherein is 1,1-cyclohexanediacetic acid or 3-isobutyl-pentanedioic acid; 2. begin to stir after reactant being heated to fusing, continue to be heated to 250 ℃～280 ℃ dehydration reaction takes place, the water that reaction generates is steamed simultaneously; 3. after reacting completely, the cooling of the material in the reactor is obtained product.
The second kind of technical scheme that realizes the object of the invention is: have following steps: 1. add reactant substituting group pentanedioic acid and sulfonic acid class catalyzer in reactor, substituting group pentanedioic acid wherein is 1,1-cyclohexanediacetic acid or 3-isobutyl-pentanedioic acid; 2. begin to stir after being heated to fusing, continue to be heated to 150 ℃～200 ℃ dehydration reaction takes place, the water that reaction generates is steamed simultaneously; 3. after reacting completely, the cooling of the material in the reactor is obtained product.
Above-mentioned steps in 1. the substituting group pentanedioic acid and the weight ratio of sulfonic acid class catalyzer be 250: 1～335: 1; Sulfonic acid class catalyzer is the vitriol oil, tosic acid or Phenylsulfonic acid, the preferred vitriol oil.
The third technical scheme that realizes the object of the invention is: have following steps: 1. add reactant substituting group pentanedioic acid, sulfonic acid class catalyzer and have the organic solvent of azeotropic band water effect in reactor, stir, substituting group pentanedioic acid wherein is 1,1-cyclohexanediacetic acid or 3-isobutyl-pentanedioic acid; 2. under agitation material is heated to boiling and dehydration reaction takes place reactant simultaneously, and by the water trap reflux water-dividing; 3. after reacting completely, in reactor, steam organic solvent; 4. the cooling of the material in the reactor is obtained product.
The organic solvent that above-mentioned steps has the effect of azeotropic band water in 1. is dimethylbenzene, benzene, toluene or hexanaphthene, preferred dimethylbenzene; The weight ratio of substituting group pentanedioic acid and organic solvent is 1: 0.5～1: 10.Sulfonic acid class catalyzer is the vitriol oil, tosic acid or Phenylsulfonic acid, the preferred vitriol oil; The weight ratio of substituting group pentanedioic acid and sulfonic acid class catalyzer is 250: 1～335: 1.The reaction times of the dehydration reaction of step in 2. is 3～18 hours.The distillation temperature of step in 3. is 120 ℃～160 ℃.
The present invention has positive effect: the reactant among (1) preparation method of the present invention is single substituting group pentanedioic acid, does not need another reactant diacetyl oxide in the Chinese patent application 00128111.9, and does not also have acetate in the resultant; Thereby reactant of the present invention and resultant be all to not corrosion of equipment, and because there is not the existence of acetate and diacetyl oxide, hexyl originally need not carry out subsequent disposal, thereby the present invention is a kind of environment-friendly type preparation method.(2) in first kind of technical scheme of the present invention, do not add any auxiliary material and directly under higher temperature, carry out dehydration reaction, though the raw materials cost reduction is more but energy consumption is higher, so the still low preparation method of comprehensive cost, particularly do not need aftertreatment, so be a kind of complete environment-friendly type preparation method.(3) in second kind of technical scheme of the present invention, though adopted sulfonic acid class catalyzer, because catalyst consumption is few, so aftertreatment is more convenient, cost is also very low, simultaneously because its temperature of reaction is more more than first kind of technical scheme reduction, so energy-conservation obvious.(4) in the third technical scheme of the present invention, when adopting sulfonic acid class catalyzer, also adopted organic solvent with the effect of azeotropic band water, because these organic solvents can be used by recovery set, so do not increase cost substantially, and, and further reduced energy consumption and cost can further reduce because the adding of organic solvent further reduces temperature of reaction.
Embodiment
(embodiment 1)
The device of present embodiment has reaction flask, water trap, agitator, thermometer and prolong, and water trap, agitator and thermometer are installed on the reaction flask, and prolong is installed on the water trap, thereby reaction flask is communicated with atmosphere.In reaction flask, drop into 50 grams 1, the 1-cyclohexanediacetic acid, heat to 180 ℃, solid begins fusing, begins after the fusing to stir and continue to be warming up to 250 ℃, this moment, dehydration reaction began, and generation water, the water of generation steams, after 6 hours, reaction finishes, and is cooled to get below 20 ℃ light yellow transparent liquid.After two hours, begin to solidify, obtain 36.2 grams 1,1-cyclohexanediacetic acid acid anhydride, yield 80%.
(embodiment 2)
The device of present embodiment is identical with embodiment 1.Drop into 50 gram 3-isobutyl-pentanedioic acids in reaction flask, heat to 40 ℃～50 ℃, solid begins fusing, begins after the fusing to stir and continue to be warming up to 270 ℃, and dehydration reaction begins, and produces water.Under this temperature of reaction, water is steamed once producing, and after 4 hours, reaction finishes, and cooling obtains 36.6 grams 1,13-isobutyl-pentanedioic acid, yield 81%.
(embodiment 3)
The device of present embodiment is identical with embodiment 1.Drop into 50 grams 1 in reaction flask, the 1-cyclohexanediacetic acid heats to 180 ℃ of degree, solid begins fusing, begin to stir and continue to be warming up to 280 ℃ of reaction beginnings after the fusing and produce water, the water of generation steams, after 3 hours, reaction finishes, be cooled to get light yellow transparent liquid below 20 ℃, after two hours, begin to solidify 36.5 grams 1,1-cyclohexanediacetic acid acid anhydride, yield 80.5%.
(embodiment 4)
The device of present embodiment is identical with embodiment 1.Drop into 50 grams 1 in reaction flask, the 1-cyclohexanediacetic acid and the 0.2 gram vitriol oil heat to 180 ℃, solid begins fusing, and the reaction beginning also produces water, and the water of generation is steamed under temperature of reaction, after 6 hours, collect 4 gram water, reaction finishes, and is cooled to get below 20 ℃ light yellow transparent liquid, after two hours, begin to solidify 44 grams 1,1-cyclohexanediacetic acid acid anhydride, yield 97%.
(embodiment 5 to embodiment 11)
Device and the preparation method of each embodiment are substantially the same manner as Example 4, and concrete material, reaction times, output and yield see Table 1.
Table 1
| The embodiment sequence number | Raw material | Sulfonic acid class catalyzer | Temperature of reaction | Reaction times | Output | Yield |
| 5 | 1.1-cyclohexanediacetic acid 50 grams | Tosic acid 0.2 gram | 160℃ | 7 hours | 42 grams | 92.5％ |
| 6 | 1.1-cyclohexanediacetic acid 50 grams | Toluenesulphonic acids 0.2 gram | 160℃ | 7 hours | 43 grams | 94.8％ |
| 7 | 1.1-cyclohexanediacetic acid 50 grams | The vitriol oil 0.15 gram | 200℃ | 5 hours | 43.5 gram | 95.9％ |
| 8 | 3-isobutyl-pentanedioic acid 50 grams | The vitriol oil 0.15 gram | 180℃ | 6 hours | 42.4 gram | 93.8％ |
| 9 | 1.1-cyclohexanediacetic acid 50 grams | The vitriol oil 0.2 gram | 150℃ | 8 hours | 42.8 gram | 94.3％ |
| 10 | 3-isobutyl-pentanedioic acid 50 grams | Tosic acid 0.2 gram | 160℃ | 7 hours | 42.2 gram | 93.5％ |
| 11 | 3-isobutyl-pentanedioic acid 50 grams | Tosic acid 0.15 gram | 160℃ | 7 hours | 42 grams | 92.9％ |
(embodiment 12)
The device of present embodiment is identical with embodiment 1.In reaction flask, throw 50 gram 1.1-cyclohexanediacetic acids, the 0.2 gram vitriol oil and 150 milliliters of toluene, stir, heat to 120 ℃ and begin to carry out dehydration reaction, produce water during reaction, tell the water of generation with water trap, be suspended in 1 in the reaction soln, the 1-cyclohexanediacetic acid dissolves gradually, after 18 hours, form flaxen homogeneous phase solution, be divided into out the water of about 2 grams, distill out toluene then, after toluene distillation is intact, temperature of charge rises to 160 ℃, is incubated 1 hour postcooling to room temperature, obtains 44.0 grams 1,1-cyclohexanediacetic acid acid anhydride, yield 97%.
(embodiment 13)
The device of present embodiment is identical with embodiment 1.In reaction flask, drop into 50 grams 1, the 1-cyclohexanediacetic acid, 0.2 the gram vitriol oil and 150 milliliters of xylol, stir, heat to the boiling material and begin to reflux, and dehydration reaction takes place, tell the water of generation in the backflow with water trap, be suspended in 1 in the reaction soln, the 1-cyclohexanediacetic acid dissolves gradually, after 2 hours, form flaxen homogeneous phase solution, through 3 to 4 hours reaction, be divided into out the water of about 4 grams, distill out xylol then, after xylol has distilled, temperature of charge rises to 160 ℃, and cooling obtains 45.0 grams 1,1-cyclohexanediacetic acid acid anhydride, yield 99%.
(embodiment 14 to embodiment 28)
Device and the preparation method of each embodiment are substantially the same manner as Example 13, and concrete material, reaction times, output and yield see Table 2.
Table 2
| The embodiment sequence number | Raw material | Sulfonic acid class catalyzer | The organic solvent milliliter | The highest distillation temperature | Reaction times hour | The output gram | Yield % |
| 14 | 1.1-cyclohexanediacetic acid 50 grams | The vitriol oil 0.2 gram | O-Xylol 150 | 160℃ | 3～4 | 45.2 | 99.5 |
| 15 | 1.1-cyclohexanediacetic acid 50 grams | The vitriol oil 0.2 gram | Xylol 28.9 | 160℃ | 3～4 | 44.8 | 98.6 |
| 16 | 1.1-cyclohexanediacetic acid 50 grams | The vitriol oil 0.2 gram | Xylol 578 | 160℃ | 3～4 | 44.5 | 97.9 |
| 17 | 1.1-cyclohexanediacetic acid 50 grams | The vitriol oil 0.2 gram | O-Xylol 29 | 160℃ | 4-5 | 44.3 | 97.5 |
| 18 | 1.1-cyclohexanediacetic acid 50 grams | The vitriol oil 0.15 gram | M-xylene 150 | 160℃ | 3.5～4. | 45 | 99.0 |
| 19 | 1.1-cyclohexanediacetic acid 50 grams | Tosic acid 0.2 gram | P-Xylol 150 | 160℃ | 4～4.5 | 44.4 | 97.7 |
| 20 | 1.1-cyclohexanediacetic acid 50 grams | Tosic acid 0.15 gram | Xylol 150 | 160℃ | 4.5～5 | 44.1 | 97.0 |
| 21 | 1.1-cyclohexanediacetic acid 50 grams | Toluenesulphonic acids 0.2 gram | Toluene 150 | 160℃ | 4～4.5 | 44.2 | 97.2 |
| 22 | 1.1-cyclohexanediacetic acid 50 grams | Toluenesulphonic acids 0.2 gram | Toluene 29 | 160℃ | 4～5 | 44.5 | 97.9 |
| 23 | 1.1-cyclohexanediacetic acid 50 grams | Toluenesulphonic acids 0.2 gram | Toluene 577 | 160℃ | 4.5-5.5 | 43.6 | 95.9 |
| 24 | 1.1-cyclohexanediacetic acid 50 grams | The vitriol oil 0.2 gram | Benzene 150 | 160℃ | 5～6 | 44.1 | 97.0 |
| 25 | 1.1-cyclohexanediacetic acid 50 grams | The vitriol oil 0.2 gram | Benzene 28 | 160℃ | 5～6 | 43.9 | 96.58 |
| 26 | 1.1-cyclohexanediacetic acid 50 grams | The vitriol oil 0.2 gram | Hexanaphthene 150 | 160℃ | 5.5～6 | 44.7 | 98.3 |
| 27 | 1.1-cyclohexanediacetic acid 50 grams | The vitriol oil 0.2 gram | Hexanaphthene 31 | 160℃ | 5.5-6.5 | 43.8 | 96.4 |
| 28 | 1.1-cyclohexanediacetic acid 50 grams | The vitriol oil 0.2 gram | Hexanaphthene 617 | 160℃ | 5.5～6 | 42.8 | 94.16 |
Among the above embodiment used xylol be by the strippings of fractionating coal tar or catalytic reforming petroleum naphtha through fractionation, or by toluene through disproportionation system.
(embodiment 29)
The device of present embodiment is identical with embodiment 1.In reaction flask, drop into 50 gram 3-isobutyl-pentanedioic acids, the 0.15 gram vitriol oil and 75 milliliters of Mixed XYLENEs, stir, heating to boiling begins to reflux, 3-isobutyl-pentanedioic acid generation dehydration reaction in the backflow, producing water together refluxes with Mixed XYLENE, tell the water of generation with water trap,, be divided into out the water of about 4.5 grams through 7 to 10 hours reaction.Distill out Mixed XYLENE then in reaction flask, after Mixed XYLENE had distilled, temperature of charge rose to 160 ℃, and cooling obtains 42.5 gram 3-isobutyl-Pyroglutaric acids, yield 94%.
(embodiment 30 to embodiment 42)
The device of each embodiment and preparation method are basic identical with embodiment 28, and concrete material, reaction times, output and yield see Table 3.
Table 3
| The embodiment sequence number | Raw material | Sulfonic acid class catalyzer | The organic solvent milliliter | The highest distillation temperature | Reaction times hour | The output gram | Yield % |
| 30 | Isobutyl-penta oxalic acid 50 grams | The vitriol oil 0.2 gram | O-Xylol 150 | 160℃ | 7～10 | 43 | 95.1 |
| 31 | Isobutyl-penta oxalic acid 50 grams | The vitriol oil 0.2 gram | Xylol 28.9 | 160℃ | 6.5～11 | 42.4 | 93.7 |
| 32 | Isobutyl-penta oxalic acid 50 grams | The vitriol oil 0.2 gram | Xylol 578 | 160℃ | 8～13 | 41 | 90.7 |
| 33 | Isobutyl-penta oxalic acid 50 grams | The vitriol oil 0.15 gram | M-xylene 150 | 160℃ | 8～11.5 | 42.1 | 92.9 |
| 34 | Isobutyl-penta oxalic acid 50 grams | Tosic acid 0.2 gram | P-Xylol 150 | 160℃ | 7～10 | 41.9 | 92.7 |
| 35 | Isobutyl-penta oxalic acid 50 grams | Tosic acid 0.15 gram | Xylol 150 | 160℃ | 7.5～11 | 41.5 | 91.7 |
| 36 | Isobutyl-penta oxalic acid 50 grams | Tosic acid 0.15 gram | M-xylene 150 | 160℃ | 7.5-11 | 41.3 | 91.3 |
| 37 | Isobutyl-penta oxalic acid 50 grams | Toluenesulphonic acids 0.2 gram | Toluene 150 | 160℃ | 8～12 | 42 | 92.8 |
| 38 | Isobutyl-penta oxalic acid 50 grams | Toluenesulphonic acids 0.2 gram | Toluene 29 | 160℃ | 7～10 | 42.3 | 93.6 |
| 39 | Isobutyl-penta oxalic acid 50 grams | Toluenesulphonic acids 0.2 gram | Toluene 577 | 160℃ | 8.5～13 | 41.9 | 92.7 |
| 40 | Isobutyl-penta oxalic acid 50 grams | The vitriol oil 0.2 gram | Benzene 150 | 160℃ | 8～10 | 42.1 | 93.1 |
| 41 | Isobutyl-penta oxalic acid 50 grams | The vitriol oil 0.2 gram | Benzene 28 | 160℃ | 7.5-12.5 | 42.2 | 93.3 |
| 42 | Isobutyl-penta oxalic acid 50 grams | The vitriol oil 0.2 gram | Hexanaphthene 150 | 160℃ | 8～12 | 42.4 | 93.8 |
| 43 | Isobutyl-penta oxalic acid 50 grams | The vitriol oil 0.2 gram | Hexanaphthene 31 | 160℃ | 7.5～11 | 42.1 | 93.1 |
| 44 | Isobutyl-penta oxalic acid 50 grams | The vitriol oil 0.2 gram | Hexanaphthene 617 | 160℃ | 8～14 | 41.4 | 91.6 |
(application examples 1)
Embodiment 14 is resultant 1, and 1-cyclohexanediacetic acid acid anhydride adds the solution that is made into by 60 gram 25% ammoniacal liquor and 100 gram water, stirring at room 2 hours, activated carbon decolorizing, filter, divide water-yielding stratum, water layer is 2 with hcl acidifying to PH, separate out white solid, filter, wash neutrality, obtain 46 grams 1 after the filter cake oven dry, 1-cyclohexanediacetic acid monoamide, yield 92%.
(application examples 2)
42.5 gram 3-isobutyl-Pyroglutaric acids of gained among the embodiment 28 are added the solution that is made into by 60 gram 25% ammoniacal liquor and 100 gram water, stirring at room 2 hours, activated carbon decolorizing filters, divide water-yielding stratum, water layer is 2 with hcl acidifying to PH, with 250 milliliters of ethyl acetate extraction twice, and the organic layer washing, dry, the vacuum desolventizing obtains 42.5 gram 3-isobutyl-glutaryl amine, yield 82%.
Describe several embodiments of the present invention above, but content of the present invention is not limited to this fully.
Claims (10)
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Claims (10)
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1, a kind of preparation method of substituting group Pyroglutaric acid has following steps: 1. add reactant substituting group pentanedioic acid in reactor, substituting group pentanedioic acid wherein is 1,1-cyclohexanediacetic acid or 3-isobutyl-pentanedioic acid; 2. begin to stir after reactant being heated to fusing, continue to be heated to 250 ℃～280 ℃ dehydration reaction takes place, the water that reaction generates is steamed simultaneously; 3. after reacting completely, the cooling of the material in the reactor is obtained product.
2, a kind of preparation method of substituting group Pyroglutaric acid has following steps: 1. add reactant substituting group pentanedioic acid and sulfonic acid class catalyzer in reactor, substituting group pentanedioic acid wherein is 1,1-cyclohexanediacetic acid or 3-isobutyl-pentanedioic acid; 2. begin to stir after being heated to fusing, continue to be heated to 150 ℃～200 ℃ dehydration reaction takes place, the water that reaction generates is steamed simultaneously; 3. after reacting completely, the cooling of the material in the reactor is obtained product.
3, the preparation method of substituting group Pyroglutaric acid according to claim 2 is characterized in that: step in 1. the substituting group pentanedioic acid and the weight ratio of sulfonic acid class catalyzer be 250: 1～335: 1; Sulfonic acid class catalyzer is the vitriol oil, tosic acid or Phenylsulfonic acid.
4, the preparation method of substituting group Pyroglutaric acid according to claim 3 is characterized in that: the 1. middle sulfonic acid class catalyzer of step is the vitriol oil.
5, a kind of preparation method of substituting group Pyroglutaric acid, have following steps: 1. in reactor, add reactant substituting group pentanedioic acid, sulfonic acid class catalyzer and have the organic solvent of azeotropic band water effect, stir, substituting group pentanedioic acid wherein is 1,1-cyclohexanediacetic acid or 3-isobutyl-pentanedioic acid; 2. under agitation material is heated to boiling and dehydration reaction takes place reactant simultaneously, and by the water trap reflux water-dividing; 3. after reacting completely, in reactor, steam organic solvent; 4. the cooling of the material in the reactor is obtained product.
6, the preparation method of substituting group Pyroglutaric acid according to claim 5 is characterized in that: the organic solvent that step has the effect of azeotropic band water in 1. is dimethylbenzene, benzene, toluene or hexanaphthene; The weight ratio of substituting group pentanedioic acid and organic solvent is 1: 0.5～1: 10.
7, the preparation method of substituting group Pyroglutaric acid according to claim 6 is characterized in that: the band water organic solvent of step in 1. is dimethylbenzene.
8, the preparation method of substituting group Pyroglutaric acid according to claim 5 is characterized in that: at the sulfonic acid class catalyzer of step in 1. is the vitriol oil, tosic acid or Phenylsulfonic acid; The weight ratio of substituting group pentanedioic acid and sulfonic acid class catalyzer is 250: 1～335: 1.
9, the preparation method of substituting group Pyroglutaric acid according to claim 8 is characterized in that: the sulfonic acid class catalyzer of step in 1. is the vitriol oil.
10, according to the preparation method of the described substituting group Pyroglutaric acid of one of claim 5 to 9, it is characterized in that: the reaction times of the dehydration reaction of step in 2. is 3～18 hours; The distillation temperature of step in 3. is 120 ℃～160 ℃.